Preparation method and application of a long-chain olefin-modified dicyclopentadiene thermopolymerized hydrogenated resin

Abstract

This invention relates to the field of petroleum resin technology, particularly to the field of IPCC08F232, and more specifically, to a method for preparing and applying a long-chain olefin-modified dicyclopentadiene thermally polymerized hydrogenated resin. The method includes the following steps: Step 1: Dicyclopentadiene, α-olefin, and a first solvent are mixed uniformly and subjected to a thermal polymerization reaction. Unreacted raw materials are removed through post-treatment to obtain the dicyclopentadiene thermally polymerized modified resin. Step 2: The dicyclopentadiene thermally polymerized modified resin and a second solvent are mixed uniformly, a catalyst is added, and a hydrogenation reaction is carried out. The resulting product is obtained through filtration and distillation. The long-chain olefin-modified dicyclopentadiene thermally polymerized hydrogenated resin prepared in this application has advantages over ordinary dicyclopentadiene thermally polymerized hydrogenated resin, including a moderate molecular weight, uniform molecular weight distribution, good compatibility with mineral oil, and strong adhesion of the prepared ink.

Description

Technical Field

[0001] This invention relates to the field of petroleum resin technology, particularly to the field of IPCC08F232, and more specifically, to a method for preparing and applying a long-chain olefin-modified dicyclopentadiene thermally hydrogenated resin. Background Technology

[0002] The ink industry has long used petroleum resins as film-forming substances. Since inks need to be dissolved in drying oils before use, they require good solubility in these oils, meaning the petroleum resin needs a high n-heptane number. Additionally, to maintain fast drying, the petroleum resin needs to maintain a low hue while also having a high softening point. Dicyclopentadiene petroleum resin is also frequently used in the ink industry due to its good oil solubility and low price. Dicyclopentadiene petroleum resin is typically produced by the thermal polymerization of dicyclopentadiene under high temperature and pressure. It is widely used in adhesives, coatings, and inks. Because dicyclopentadiene resin has poor thermal stability and is prone to color change at high temperatures, hydrogenation is used to saturate the double bonds in the resin to improve its stability. However, because dicyclopentadiene resin mainly has a cyclic structure with cyclopentadiene as the unit, a large molecular weight, uneven molecular weight distribution, and a lack of aliphatic hydrocarbon components, it has poor compatibility with mineral oils in ink formulations, resulting in insufficient ink adhesion and limiting its use.

[0003] CN105085815B discloses an α-olefin-dicyclopentadiene copolymer and its preparation method. This invention uses a diamine-based non-metallocene catalyst as the catalyst to catalyze the copolymerization of α-olefins and dicyclopentadiene. Such non-metallocene catalysts are simple to synthesize, have good stability, and a wide range of tunable structures. Using a diamine-based non-metallocene catalyst to catalyze the copolymerization of dicyclopentadiene with longer-chain α-olefins (1-butene, 1-hexene, or 1-octene, etc.) results in copolymers with good solubility and processability. The polymerization process of this invention is simple and easy to control, which is beneficial for industrial applications. However, the molecular weight, molecular weight distribution, and compatibility with inks of the resin were not investigated. Summary of the Invention

[0004] The first aspect of this invention provides a method for preparing a long-chain olefin-modified dicyclopentadiene thermally hydrogenated resin, comprising the following steps:

[0005] Step 1: Mix dicyclopentadiene, α-olefin and the first solvent evenly, carry out thermal polymerization reaction, and remove unreacted raw materials after post-treatment to obtain dicyclopentadiene thermally modified resin.

[0006] Step 2: Mix the dicyclopentadiene thermally modified resin and the second solvent evenly, add the catalyst, carry out the hydrogenation reaction, and obtain the product by filtration and distillation.

[0007] The thermal polymerization reaction is carried out in an inert gas atmosphere, wherein the inert gas includes one of nitrogen and helium.

[0008] The α-olefin has 8-30 carbon atoms.

[0009] The α-olefin includes at least one selected from 1-nonene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.

[0010] Preferably, the α-olefin includes at least one selected from 1-nonene, 1-dodecene, and 1-hexadecene.

[0011] The purity of the dicyclopentadiene is 85-99%, and the weight ratio of the dicyclopentadiene to the α-olefin is (70-90):(10-30).

[0012] Since dicyclopentadiene resin is mainly a cyclic structure with cyclopentadiene as the unit and lacks aliphatic hydrocarbon components, it has poor compatibility with mineral oil and other components when used in ink formulations. The applicant's research found that by introducing long-chain α-olefins to modify dicyclopentadiene resin, the compatibility with ink components can be effectively improved. At the same time, limiting the weight ratio of dicyclopentadiene to α-olefins to (70-90):(10-30) can further improve its adhesion (GB / T1720-2020 paint film cross-cut test) to level 2. This may be because the long-chain alkyl structure has similar polarity to aliphatic compounds such as mineral oil, which promotes dispersion in the ink system.

[0013] Due to the introduction of long-chain alkyl compounds, the limited mobility of long chains can easily lead to uneven molecular weight and molecular weight distribution during the reaction. Further research by the applicant revealed that a thermal polymerization reaction with a pressure of 0.5-1.5 MPa, a temperature of 140-250 °C, and a time of 4-8 h can effectively improve the uniformity of molecular weight distribution, resulting in a molecular weight distribution of dicyclopentadiene thermally modified resin below 2.0. This may be because specific reaction conditions balance the reaction rate and grafting efficiency.

[0014] Preferably, the weight ratio of the dicyclopentadiene to the α-olefin is (80-90):(10-20).

[0015] The first solvent and the second solvent are both selected from at least one of octane, nonane, decane, toluene, xylene, trimethylbenzene, n-hexane, cyclohexane and n-heptane.

[0016] Preferably, both the first solvent and the second solvent are selected from at least one of toluene, xylene, trimethylbenzene, n-hexane, cyclohexane, and n-heptane.

[0017] The weight ratio of the dicyclopentadiene to the first solvent is 100:(50-250).

[0018] Preferably, the weight ratio of the dicyclopentadiene to the first solvent is 100:(55-250).

[0019] The weight ratio of the dicyclopentadiene thermally modified resin, the second solvent, and the catalyst is 100:(50-150):(0.5-3).

[0020] Preferably, the weight ratio of the dicyclopentadiene thermally modified resin, the second solvent, and the catalyst is 100:(50-150):(0.8-2).

[0021] The thermal polymerization reaction is carried out at a pressure of 0.5-1.5 MPa, a temperature of 140-250℃, and a time of 4-8 hours.

[0022] Preferably, the pressure of the thermal polymerization reaction is 0.5-1.5 MPa, the temperature is 140-220°C, and the time is 4-7 h; the pressure of the hydrogenation reaction is 1.4-2.5 MPa, the temperature is 150-200°C, and the time is 4-10 h.

[0023] Preferably, the hydrogenation reaction is carried out at a pressure of 1.4-2 MPa, a temperature of 150-180°C, and a time of 5-8 h.

[0024] The second aspect of this invention provides an application of a method for preparing a long-chain olefin-modified dicyclopentadiene thermally hydrogenated resin, which is used in the preparation of inks.

[0025] Preferably, the amount of resin added to the ink is 5-20 wt%.

[0026] Beneficial effects:

[0027] 1. Modifying dicyclopentadiene resin by introducing long-chain α-olefins can effectively improve its compatibility with ink components.

[0028] Compatibility

[0029] 2. Limiting the weight ratio of dicyclopentadiene to α-olefin to (70-90):(10-30) can further improve its adhesion (GB / T1720-2020 paint film scratch test) to level 2.

[0030] 3. The pressure of the thermal polymerization reaction is 0.5-1.5 MPa, the temperature is 140-250℃, and the time is 4-8 h, which can effectively improve the uniformity of molecular weight distribution, so that the molecular weight distribution of the dicyclopentadiene thermally modified resin is lower than 2.0.

[0031] 4. The resin prepared in this application has a low softening point (below 125°C) and a number-average molecular weight of no more than 1000, which can be matched with ink systems. Detailed Implementation

[0032] Example 1

[0033] A method for preparing a long-chain olefin-modified dicyclopentadiene thermopolymerized hydrogenated resin comprises the following steps:

[0034] (1) Polymerization: Dicyclopentadiene (produced by Guangdong Xinhua Yue Resin Co., Ltd.) with a purity of 90% was added to a 2L stainless steel thermopolymerization reactor at a mass ratio of 1-dodecene:toluene = 90:10:100. After removing the air in the reactor by multiple nitrogen purgings, the pressure was increased to 0.5MPa. After stirring, the temperature was raised and the reaction was carried out at 180℃ for 6 hours. After the container cooled to room temperature, the resin liquid after the reaction was transferred to a distillation flask and the unreacted olefins and toluene solvent were removed by vacuum distillation to obtain long-chain olefin modified dicyclopentadiene thermopolymerization resin.

[0035] (2) Hydrogenation: The long-chain olefin modified dicyclopentadiene thermopolymer resin obtained in step (1) is added to a 2L stainless steel hydrogenation reactor with toluene and nickel-supported catalyst (SNCAT-6210P type produced by Shanghai Xunkai Catalysis Co., Ltd., with nickel content ≥55%, the same below) in a mass ratio of 100:120:1. The air in the hydrogenation reactor is removed by purging with hydrogen gas multiple times. After stirring, the temperature is raised to 160℃ and then hydrogen gas is introduced to pressurize to 1.3MPa. After hydrogenation for 4 hours, the pressure is released by cooling and depressurization. Toluene is removed by vacuum distillation to obtain the final product.

[0036] Example 2

[0037] A method for preparing a long-chain olefin-modified dicyclopentadiene thermopolymerized hydrogenated resin comprises the following steps:

[0038] (1) Polymerization: Dicyclopentadiene (produced by Guangdong Xinhua Yue Resin Co., Ltd.) with a purity of 95% was added to a 2L stainless steel thermopolymerization reactor in the mass ratio of 1-nonene:xylene = 85:15:130. After removing the air in the reactor by nitrogen purging several times, the pressure was increased to 0.8MPa. After stirring, the temperature was raised and the reaction was carried out at 200℃ for 4 hours. After the container cooled to room temperature, the resin liquid after the reaction was transferred to a distillation flask and the unreacted olefins and xylene solvent were removed by vacuum distillation to obtain long-chain olefin modified dicyclopentadiene thermopolymerization resin.

[0039] (2) Hydrogenation: The long-chain olefin modified dicyclopentadiene thermopolymer resin obtained in step (1) is added to a 2L stainless steel hydrogenation reactor with xylene and nickel-supported catalyst in a mass ratio of 100:150:2. The air in the hydrogenation reactor is removed by purging with hydrogen gas multiple times. After stirring, the temperature is raised to 150°C and then hydrogen gas is introduced to pressurize to 1.5MPa. After hydrogenation for 6 hours, the pressure is released by cooling and the xylene is removed by vacuum distillation to obtain the final product.

[0040] Example 3

[0041] A method for preparing a long-chain olefin-modified dicyclopentadiene thermopolymerized hydrogenated resin comprises the following steps:

[0042] (1) Polymerization: Dicyclopentadiene (produced by Guangdong Xinhua Yue Resin Co., Ltd.) with a purity of 99% was added to a 2L stainless steel thermopolymerization reactor at a mass ratio of 1-hexadecimal:cyclohexane = 80:20:200. After removing the air in the reactor by multiple nitrogen purgings, the pressure was increased to 1.5MPa. After stirring, the temperature was raised and the reaction was carried out at 140℃ for 7 hours. After the container cooled to room temperature, the resin liquid after the reaction was transferred to a distillation flask and the unreacted olefins and cyclohexane solvent were removed by vacuum distillation to obtain long-chain olefin modified dicyclopentadiene thermopolymerization resin.

[0043] (2) Hydrogenation: The long-chain olefin modified dicyclopentadiene thermopolymer resin obtained in step (1) is added to a 2L stainless steel hydrogenation reactor in a mass ratio of 100:80:3. The air in the hydrogenation reactor is removed by purging with hydrogen gas multiple times. After stirring, the temperature is raised to 180°C and then hydrogen gas is introduced to pressurize to 2.0 MPa. After hydrogenation for 8 hours, the pressure is released by cooling and distillation under reduced pressure to remove cyclohexane.

[0044] Example 4

[0045] A method for preparing a long-chain olefin-modified dicyclopentadiene thermopolymerized hydrogenated resin comprises the following steps:

[0046] (1) Polymerization: Add 85% pure dicyclopentadiene (produced by Guangdong Xinhua Yue Resin Co., Ltd.) to a 2L stainless steel thermopolymerization reactor in the mass ratio of 1-nonene: n-hexane = 85:15:50. After removing the air in the reactor by nitrogen purging several times, pressurize to 1.0MPa, start stirring and heat up, and react at 220℃ for 4h. After the container cools to room temperature, transfer the resin liquid after reaction to a distillation flask and remove the unreacted olefins and n-hexane solvent by vacuum distillation to obtain long-chain olefin modified dicyclopentadiene thermopolymerization resin.

[0047] (2) Hydrogenation: The long-chain olefin modified dicyclopentadiene thermopolymer resin obtained in step (1) is added to a 2L stainless steel hydrogenation reactor with hexane and nickel-supported catalyst in a mass ratio of 100:50:0.8. The air in the hydrogenation reactor is removed by purging with hydrogen gas multiple times. After stirring, the temperature is raised to 165°C and then hydrogen gas is introduced to pressurize to 1.4MPa. After hydrogenation for 5 hours, the pressure is released by cooling and depressurization. Hexane is removed by vacuum distillation to obtain the final product.

[0048] Comparative Example 1

[0049] A method for preparing a dicyclopentadiene thermally hydrogenated resin comprises the following steps:

[0050] (1) Polymerization: Add dicyclopentadiene (produced by Guangdong Xinhua Yue Resin Co., Ltd.) with a purity of 85% and xylene = 100:130 to a 2L stainless steel thermopolymerization reactor. After removing the air in the reactor by multiple nitrogen purgings, pressurize to 0.8MPa, start stirring and heat up to 200℃ for 4 hours. After the container cools to room temperature, transfer the resin liquid after reaction to a distillation flask and remove the unreacted olefins and xylene solvent by vacuum distillation to obtain dicyclopentadiene thermopolymerization resin.

[0051] (2) Hydrogenation: The dicyclopentadiene thermopolymer resin obtained in step (1) is added to a 2L stainless steel hydrogenation reactor in a mass ratio of 100:120:2. The air in the hydrogenation reactor is removed by purging with hydrogen gas multiple times. After stirring, the temperature is raised to 150°C and then hydrogen gas is introduced to pressurize to 1.5MPa. After hydrogenation for 6 hours, the pressure is released by cooling and depressurization. The xylene is removed by vacuum distillation to obtain the final product.

[0052] Comparative Example 2

[0053] A method for preparing a dicyclopentadiene thermally hydrogenated resin comprises the following steps:

[0054] (1) Polymerization: Add 99% pure dicyclopentadiene (produced by Guangdong Xinhua Yue Resin Co., Ltd.) to n-hexane in a 2L stainless steel thermopolymerization reactor at a mass ratio of 100:50. After removing the air in the reactor by nitrogen purging several times, pressurize to 1.0MPa, start stirring and heat up to 220℃ for 4 hours. After the container cools to room temperature, transfer the resin liquid after reaction to a distillation flask and remove the unreacted olefin and n-hexane solvent by vacuum distillation to obtain dicyclopentadiene thermopolymerization resin.

[0055] (2) Hydrogenation: The dicyclopentadiene thermopolymer resin obtained in step (1) is added to a 2L stainless steel hydrogenation reactor with hexane and nickel-supported catalyst in a mass ratio of 100:50:0.8. The air in the hydrogenation reactor is removed by purging with hydrogen gas multiple times. After stirring, the temperature is raised to 165°C and then hydrogen gas is introduced to pressurize to 1.4MPa. After hydrogenation for 5 hours, the pressure is released by cooling and depressurization. Hexane is removed by vacuum distillation to obtain the final product.

[0056] Performance testing methods

[0057] Performance tests were conducted on the examples and comparative examples, and the test data are listed in Table 1.

[0058] 1. Resin performance tests, the results are shown in Table 1. Among them, softening point: determined by the ring and ball method specified in GB / T2294-2019; molecular weight and molecular weight distribution: determined by gel permeation chromatography using Agilent 1260 Infinity II GPC, with polystyrene as the molecular weight standard; n-heptane capacity: determined by the method for determining n-heptane capacity in Appendix B of GB / T24138-2009.

[0059] 2. Ink Adhesion Test: The ink was prepared according to the formula (weight percentage) in Table 2, and the test results are shown in Table 3. The GB / T1720-2020 paint film cross-cut test was used for evaluation. Seven parts (1 / 2 / 3 / 4 / 5 / 6 / 7) were marked on the upper side of the roller line, and they were divided into 7 grades, with grade 1 being the best and grade 7 being the worst.

[0060] Performance test data

[0061] Table 1 Table 2

[0062] Raw material name Mixing ratio (wt%) carbon black 5.0 Calcium carbonate 30.0 Flaxseed oil 40.0 High-boiling-point kerosene 10.0 resin 15.0

[0063] Table 3

[0064] project Adhesion (Grade) Example 1 2 Example 2 2 Example 3 2 Example 4 2 Comparative Example 1 5 Comparative Example 2 6

Claims

1. A method for preparing a long-chain olefin-modified dicyclopentadiene thermally hydrogenated resin, characterized in that, Includes the following steps: (1) Polymerization: Dicyclopentadiene: 1-nonene: xylene with a purity of 95% was added to a 2L stainless steel thermopolymerization reactor in a mass ratio of 85:15:

130. After removing the air in the reactor by multiple nitrogen purgings, the pressure was increased to 0.8MPa. Stirring was started and the temperature was raised. The reaction was carried out at 200℃ for 4 hours. After the container cooled to room temperature, the resin solution after the reaction was transferred to a distillation flask. Unreacted olefins and xylene solvent were removed by vacuum distillation to obtain long-chain olefin modified dicyclopentadiene thermopolymerization resin. (2) Hydrogenation: The long-chain olefin modified dicyclopentadiene thermopolymer resin obtained in step (1) is added to a 2L stainless steel hydrogenation reactor with xylene and nickel-supported catalyst in a mass ratio of 100:150:

2. The air in the hydrogenation reactor is removed by purging with hydrogen gas multiple times. After stirring, the temperature is raised to 150°C and then hydrogen gas is introduced to pressurize to 1.5MPa. After hydrogenation for 6 hours, the pressure is released by cooling and the xylene is removed by vacuum distillation to obtain the final product.

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